Uranium Isotopic Fractionation Induced by U(VI) Adsorption onto Common Aquifer Minerals

Uranium groundwater contamination due to U mining and processing affects numerous sites globally. Bioreduction of soluble, mobile U(VI) to U(IV)-bearing solids is potentially a very effective remediation strategy. Uranium isotopes (²³⁸U/²³⁵U) have been utilized to track the progress of microbial reduction, with laboratory and field studies finding a ∼1‰ isotopic fractionation, with the U(IV) product enriched in ²³⁸U. However, the isotopic fractionation produced by adsorption may complicate the use of ²³⁸U/²³⁵U to trace microbial reduction. A previous study found that adsorption of U(VI) onto Mn oxides produced a -0.2‰ fractionation with the adsorbed U(VI) depleted in ²³⁸U. In this study, adsorption to quartz, goethite, birnessite, illite, and aquifer sediments induced an average isotopic fractionation of -0.15‰ with the adsorbed U(VI) isotopically lighter than coexisting aqueous U(VI). In bicarbonate-bearing matrices, the fractionation depended little on the nature of the sorbent, with only birnessite producing an atypically large fractionation. In the case of solutions with ionic strengths much lower than those of typical groundwater, less isotopic fractionation was produced than U(VI) solutions with greater ionic strength. Studies using U isotope data to assess U(VI) reduction must consider adsorption as a lesser, but significant isotope fractionation process.